DE60023614T2 - Transparent electrolytic structure and process for its preparation, coating fluid therefor and display device having this structure - Google Patents

Description

1. Field of the invention

The The present invention relates to a transparent conductive layered structure with a transparent substrate, a transparent conductive layer and a transparent coating layer, which are formed in this sequence on the substrate, in the front panel, etc. of CRT, etc., displays. Especially The present invention relates to a transparent conductive layer structure with excellent film strength, weather resistance, conductivity etc. of the transparent conductive Layers, and with which a reduction in production costs is expected. The present invention also relates to a process for producing the same onto a coating liquid for forming a transparent coating layer and on a coating liquid for forming a transparent conductive layer which is in this Manufacturing process can be used. The present invention further relates to a display comprising this transparent conductive layer structure used.

2. Description of the state of the technique

In addition to the ability to to easily recognize the display screen, and thereby a visual fatigue there is a need for cathode ray tubes (CRTs) today, which are used as computer displays, etc., with which it no adhesion of dust or electric shock due to electrostatic Charging the CRT screen gives.

Furthermore There has been concern over harmful effects in recent years from low frequency electromagnetic waves to the human Body, which are generated by CRTs. It is preferable that these types from electromagnetic waves do not escape to the outside.

Furthermore have been in recent Time problems with the same electrostatic charge and the Leakage of electromagnetic waves as in CRTs for plasma display panels (PDPs) used in wall mounted televisions become.

It is possible, this leakage of electromagnetic waves, for example, by Forming a transparent conductive To prevent layer on the front panel of the display.

The above-mentioned method for preventing the above-mentioned leakage of electromagnetic waves is theoretically the same as countermeasures recently taken to prevent electrostatic charging. However, the aforementioned transparent conductive layer is required to have a much higher conductivity than conductive layers formed to prevent electrostatic charging (10 ⁸ to 10 ¹⁰ Ω / □ in terms of surface resistance).

That is, it is necessary to provide a transparent conductive layer having at least a low resistance of 10 ⁶ Ω / □ (ohms per square) or less, preferably 5 × 10 ³ Ω / □ or less, particularly 10 ³ Ω / □ or less to prevent leakage of electromagnetic waves (electrical shielding) from CRTs. A resistance of, for example, 10 Ω / □ or less is needed in PDPs.

• (1) das Verfahren zum Aufbringen und Trocknen einer Beschichtungsflüssigkeit zum Bilden einer transparenten leitfähigen Schicht von leitfähigen Oxidmikroteilchen wie Indium-Zinn-Oxid (ITO) etc. oder in einem Lösungsmittel dispergierten Mikroteilchen auf den Frontpaneelen eines CRT und dann Backen desselben bei einer Temperatur von etwa 200°C, um die zuvor genannte transparente leitfähige Schicht zu bilden,
• (2) das Verfahren des Bildens eines transparenten leitfähigen Zinnoxid-Films (NESA Film) auf der zuvor genannten Paneeloberfläche durch eine chemische Gasphasenabscheidung (CVD) von Zinnchlorid bei hoher Temperatur,
• (3) das Verfahren des Bildens eines transparenten leitfähigen Films aus Indium-Zinn-Oxid und Titaniumoxynitrid auf einem Frontpaneel durch Sputtern,

und dergleichen wurden für CRTs vorgeschlagen.In addition, there have been various suggestions to deal with the aforementioned electrical shielding. For example, were

• (1) The method of applying and drying a coating liquid to form a transparent conductive layer of conductive oxide microparticles such as indium tin oxide (ITO), etc., or microparticles dispersed in a solvent on the front panels of a CRT and then baking it at a temperature of about 200 ° C to form the aforementioned transparent conductive layer,
• (2) the method of forming a transparent conductive tin oxide film (NESA film) on the above-mentioned panel surface by high-temperature chemical vapor deposition (CVD) of stannous chloride,
• (3) the method of forming a transparent conductive film of indium tin oxide and titanium oxynitride on a front panel by sputtering,

and the like have been proposed for CRTs.

• (4) das Verfahren zum Bilden eines leitfähigen Films durch Platzieren eines leitfähigen Netzes aus Metall oder metallbeschichteten Fasern auf der Seite des Vorrichtungskörpers eines Frontpaneels eines PDP,
• (5) das Verfahren, wobei ein durch Sputtern eines Metalls wie Silber etc. hergestellter transparenter leitfähiger Film auf dem zuvor genannten Paneel gebildet wird,

und dergleichen für PDPs vorgeschlagen.In addition, were

• (4) The method of forming a conductive film by placing a conductive mesh of metal or metal-coated fibers on the side of the device body of a front panel of a PDP,
• (5) the method wherein a transparent conductive film prepared by sputtering a metal such as silver, etc., is formed on the aforementioned panel,

and the like proposed for PDPs.

It However, there is a problem with method (4) for PDPs by having a conductive network is used, the surface resistance and also the transmittance low is. There is also a problem in creating a moiré pattern and a problem the process of forming a conductive film is complex and the costs are high.

in the In contrast, method (1) is much easier for CRTs and the manufacturing costs are lower than in the methods (2), (3) and (5), whereby a transparent conductive film by CVD or sputtering is formed. Consequently, the method under (1) which is a coating liquid used to form a transparent conductive layer, very advantageous for the aforementioned CRTs as well as for PDPs.

However, the surface resistance of the film obtained is 10 ⁹ to 10 ⁶ Ω / □ high and is insufficient for blocking the leakage of electric field with a coating liquid for forming a transparent conductive layer by method (1) containing conductive oxide microparticles Indium tin oxide (ITO) etc. used.

On the other hand, the transmittance of the obtained film using a coating liquid for forming a transparent conductive layer using metal microparticles is low, as compared with the coating liquid using ITO, because the metal microparticles are not transparent. However, since the metal microparticle layer assumes a network structure during film formation after application, the reduction in the above transmittance is small, and a low-resistance film of 10 ² to 10 ³ Ω / □ is obtained. As a result, this process is considered as a process with good prospects for the future.

Furthermore are the metal microparticles used for the aforementioned coating liquid be used to form a transparent conductive layer, on precious metals like silver, gold, platinum, rhodium, palladium etc. limited, which hardly oxidize in air, as in the Japanese For example, Japanese Patent Laid-Open No. Hei 8-77832 and Japanese Laid-Open Patent Publication No. Hei Patent No. Hei 9-55175 is shown. This is because if other metal microparticles than a noble metal such as iron, nickel, Cobalt etc. is used, getting an oxide film on the surface of this Forms metal microparticles in a surrounding air atmosphere and good conductivity as transparent conductive Layer is not preserved.

If about that addition, the resistivity of the aforementioned silver, gold, Platinum, rhodium, palladium etc. is the specific one Resistance of platinum, rhodium and palladium with 10.6, 5.1 respectively and 10.8 μΩ · cm high, compared to the 1.62 and 2.2 μΩ · cm of Silver and Gold. Consequently, the use of gold particles and Silver particles for forming a transparent conductive layer with low surface resistance prefers. As a result, silver microparticles and gold microparticles etc. mainly used as the aforementioned microparticles.

If However, when silver microparticles are used, there is a problem with the weather resistance by there is a noticeable sulphurization, oxidation and impairment by alkali, ultraviolet rays, etc. Consequently, gold became containing noble metal microparticles such as gold-coated silver microparticles which the surface the silver microparticle is coated with gold, etc., and alloy microparticles, etc. made of gold and a precious metal other than gold (like Silver, etc.) are also shown.

On the other hand, for example, a glare retreat is performed on the surface of the front panel of CRTs to prevent reflection on the screen, so that the display screen is easy to recognize. This blend treatment is performed by the method by increasing a diffuse reflection at the surface by introducing fine irregularities into the surface. However, it can not be considered that this method is very desirable because the image quality drops due to a reduction in resolution when it is used. Consequently, it is preferable that, instead, a blend-free treatment is performed by the interference method, whereby the refractive index of the transparent film and the film thickness are controlled so that there is a canceling interference of reflected light to the incident light. In order to obtain low-reflectivity results by this type of interference method, a two-layered film is generally used, the optical film thickness of a high refractive index film and a low refractive index film are respectively set to ¼λ and ¼λ or ½λ and ¼λ. A film consisting of the aforementioned indium tin oxide (ITO) microparticles is also used as this type of high refractive index film.

In addition, of the optical constants of metals (n - ik, n: refractive index, i ² = -1, k: extinction coefficient), the value of n is small, but the value of k is very high in comparison with ITO, etc. Accordingly, even if a transparent conductive layer consisting of metal microparticles is used, the same anti-reflection results as with ITO are obtained by the interference with light through the two-layered film.

There However, gold is chemically inert, there is a problem with transparent conductive Layers, which by a coating liquid for forming a transparent conductive Layer were formed containing the aforementioned gold microparticles or gold-containing noble metal microparticles as metal microparticles Use it by making the bond between these gold microparticles difficult or gold-containing noble metal microparticles and a binder matrix of silica, etc. Consequently, the film strength and the weather resistance the formed transparent conductive layers insufficient.

SUMMARY OF THE INVENTION

The The present invention focuses on these problems. you The aim is to have a transparent conductive layer structure with excellent Film strength, weather resistance, conductivity etc. of the transparent conductive Show layers.

One Another object of the present invention is to provide a method for Production of a transparent conductive layer structure with excellent Film strength, weather resistance, Conductivity, etc. of the transparent conductive Show layers.

Yet Another object of the present invention is to provide a coating liquid for forming a transparent coating layer show in the aforementioned method of preparation a transparent conductive Layer structure can be used.

Furthermore It is another object of the present invention to provide a coating liquid to show a transparent conductive layer, in the aforementioned process for producing a transparent conductive Layer structure can be used.

Furthermore It is another object of the present invention to provide a display show, with which the surface reflection the display screen is controlled and the one long-lasting has high electrical shielding effect.

That is, the present invention is a transparent conductive layered structure comprising a transparent substrate, a transparent conductive layer and a transparent coating layer, wherein the transparent conductive layer and the transparent coating layer are formed on the transparent substrate in this order. The major components of the aforementioned transparent conductive layer are gold microparticles or gold-containing noble metal microparticles containing 5% by weight or more of gold having an average particle diameter of 1 to 100 nm and a binder matrix comprising at least one functional group selected from mercapto groups (US Pat. -SH), sulfide groups (-S-) and polysulfide groups (-S _x -, x ≥ 2).

In addition, the first method for producing this transparent conductive layer structure includes the steps of applying a coating liquid for forming a transparent conductive layer whose main components are a solvent and gold microparticles or gold-containing noble metal microparticles containing 5 wt% or more of gold having an average particle diameter from 1 to 100 nm and dispersed in this solvent on a transparent substrate, then applying a coating liquid to form a transparent coating layer, whose main components are a functional group-containing compound having at least one functional group selected from mercapto groups (-SH), sulfide groups (-S-) and polysulfide groups (-S _x -, x ≥ 2) are selected, are a binder and a solvent, and conducting a heat treatment.

In addition, the second manufacturing method comprises the steps of applying a Be A coating liquid for forming a transparent conductive layer whose main components are a solvent and gold microparticles or gold-containing noble metal microparticles containing 5% by weight or more of gold having an average particle diameter of 1 to 100 nm and a functional group-containing compound having at least one functional groups selected from mercapto groups (-SH), sulfide groups (-S-) and polysulfide groups (-S _x -, x ≥ 2) and dispersed in this solvent on a transparent substrate, then applying a coating liquid to form a transparent coating layer whose main components are a binder and a solvent, and performing a heat treatment.

Next, the coating liquid for forming the transparent coating layer used in the above-mentioned first production method comprises as its main components a solvent, a binder and a functional group-containing compound having at least one functional group selected from mercapto groups (-SH), sulfide groups (-S-) and polysulfide groups (-S _x -, x ≥ 2), wherein the mixing ratio of the binder and the functional group-containing compound is 0.1 to 50 parts by weight of the functional group-containing compound per 100 parts by weight of the binder.

Moreover, the coating liquid for forming the transparent conductive layer used in the second production method comprises as its main components a solvent and gold microparticles or gold-containing noble metal microparticles containing 5% by weight or more of gold having an average particle diameter of 1 to 100 and a functional group-containing compound having at least one functional group selected from mercapto groups (-SH), sulfide groups (-S-) and polysulfide groups (-S _x -, x ≥ 2) and dispersed in this solvent.

Furthermore For example, the aforementioned display device comprises a display body and a front panel placed at the front of the same body was, wherein the aforementioned transparent conductive layer structure as the aforementioned front panel with the transparent two-layered Film side of the same on the outside has been used.

BRIEF DESCRIPTION OF THE DRAWINGS

1 FIG. 15 is a graph showing the reflection profile of the transparent conductive layer structure of Example 1. FIG.

2 Fig. 12 is a graph showing the transmission profile of the transparent conductive layer structure of Example 1.

3 FIG. 12 is a graph showing the reflection profile of the transparent conductive layer structure of Example 12. FIG.

4 FIG. 10 is a graph showing the transmission profile of the transparent layer structure of Example 12. FIG.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The The present invention will now be described in detail.

The present invention is based on the following concepts:
First, gold is chemically stable and has excellent weather resistance, chemical resistance, oxidation resistance, etc. In addition, its resistivity is low and similar to silver and copper. Consequently, both good conductivity and high chemical stability of the transparent conductive layer result when gold microparticles or gold-containing noble metal microparticles are used as metal microparticles of the aforementioned transparent conductive layer.

There However, gold is chemically inert, there is a problem by the binding between the binder matrix such as silica, etc., and the gold microparticles or gold-containing noble metal microparticles is weak. When As a result, there is a reduction in film strength and weather resistance the transparent conductive layer, the gold microparticles or gold-containing noble metal microparticles used as the aforementioned metal microparticles.

Thereafter, the present invention focuses on the formation of a relatively strong bond between gold and functional groups such as mercapto groups (-SH), sulfide groups (-S-) and polysulfide groups (-S _x -, x ≥ 2), etc.

That is, by using a binder matrix comprising at least one functional group selected from mercapto groups (-SH), sulfide groups (-S-) and polysulfide groups (-S _x -, x ≥ 2) in the transparent conductive layer It is possible to remarkably improve the film strength, weatherability, etc. of the transparent conductive layer because the gold microparticles or gold-containing noble metal microparticles bind with these functional groups to solidify the bond at the interface in the binder matrix with the gold microparticles or gold-containing noble metal microparticles.

The binder matrix comprising the aforementioned functional groups here uses a functional group-containing compound having at least one functional group consisting of mercapto groups (-SH), sulfide groups (-S-) and polysulfide groups (-S _x -, x ≥ 2) [γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3- (2-acetoxyethylthiopropyl) dimethoxymethylsilane, bis (triethoxysilylpropyl) tetrasulfane, thiomalic acid, thiosalicylic acid, thiodiglycolic acid, etc.] and resin binders or inorganic binders, and is obtained by solidification of these binders receive. Moreover, the binder matrix having the aforementioned functional groups comprises the aforementioned functional groups as a structural component of the binder matrix, the functional group-containing compound, and the resin binder or inorganic binders joined together, or the binder matrix comprises the above said functional groups, with the aforementioned functional group-containing compound which is mixed in the aforementioned binder matrix without being bound, and the resin binder or inorganic binder which are bonded together.

The aforementioned state is preferable in terms of strength. That is, it is preferable in terms of strength because, when in addition to the aforementioned functional groups such as mercapto groups (-SH), sulfide groups (-S-), polysulfide groups (-S _x -, x ≥ 2), etc. hydrolyzable Alkoxysilyl groups or functional groups which are obtained by hydrolysis of alkoxysilyl groups [-SiR ¹ _x (OR ² ) _y , R ¹ and R ² are C _n H _{2n + 1} , n = 0 to 4, x = 0 to 2, y = 3 x] are contained in the molecules of the functional group-containing compound, these functional groups firmly bond with the silica when a silica sol is used as a binder (that is, the aforementioned functional group-containing compound and the binder are joined). The bond at the interface in the silica matrix binder with the gold microparticles or gold-containing noble metal microparticles is solidified.

For example, when a transparent conductive layer (hereinafter referred to as Comparative Example 1) consisting of gold and silver two-component microparticles (that is, gold-containing noble metal microparticles) and silica is released, deterioration occurs in one to two months and there will be a marked increase in surface resistance of the transparent conductive film as a result of exposure to rain and ultraviolet rays in the sunlight. In contrast, when it is laid aside for three months or longer, there is no change in the transparent conductive layer, indicating that the weather resistance in the case of a transparent conductive layer (hereinafter referred to as Example 1) is excellent uses a binder matrix of silica comprising mercapto groups (-SH) and trimethoxysilyl groups [-Si (OCH ₃ ) ₃ ] (in fact, the functional group [-Si (OH) ₃ ] becomes a conductive liquid as a result of hydrolysis in the coating liquid As shown, moreover, in Table 4, the transparent conductive layer comprising the binder matrix of silica comprising mercapto groups (-SH) and trimethoxysilyl groups [-Si (OCH ₃ ) ₃ ] had better film strength than the transparent conductive ones Layer, which used a binder matrix of silicon oxide, the above-mentioned functional groups n not included.

The Gold microparticles or gold-containing noble metal microparticles have to in the present invention, an average particle diameter from 1 to 100 nm. If they are smaller than 1 nm, will make it difficult to make these microparticles and they will not for the convenient use, because they immediately in the coating liquid aggregate. If she's over it beyond greater than 100 nm, the transmittance becomes for visible Light of the formed transparent conductive layer too low, and even if the film thickness is decreased, the transmittance for visible To increase light, becomes the surface resistance too high and not for be practical.

Incidentally, the term average particle diameter used herein is the average particle diameter of the microparticles observed by a transmission electron microscope (TEM) has been.

Furthermore should the gold content in the aforementioned gold-containing noble metal microparticles in a range of 5% by weight or more, preferably 5 to 95% by weight and most preferably in a range of 50 to 95% by weight become. This happens because if the gold content is less than 5% by weight, it will happen that the effect of the gold is weak is and the weather resistance impaired will be while, if the content exceeds 95% by weight, it's a few economic Advantages of using gold-containing noble metal microparticles instead of gold microparticles.

Next, the coating solution of the present invention comprising gold-containing noble metal microparticles (gold-coated silver microparticles) using the gold-containing noble metal microparticles as metal microparticles can be prepared, for example, by the following method:
That is, after preparing a colloidal dispersion of silver microparticles by conventional methods [e.g., the Carey-Lea method, Am. J. Sci., 37, 47 (1889), Am. J. Sci., 38 (1889)], a reducing agent such as hydrazine, etc. and an aurate are added to this dispersion to coat the silver microparticles with gold and to obtain a dispersion of gold-containing noble metal microparticles (gold-coated silver microparticles). Incidentally, if necessary, a trace of dispersant may be added to one or both of the colloidal dispersion of silver microparticles and the aurate solution.

It it is preferred that the electrolyte concentration of the dispersion then through a procedure such as dialysis, electrodialysis, ion exchange, Ultrafiltration etc. is reduced. This happens because the colloid generally aggregated with the electrolyte when the electrolyte concentration is not reduced. This phenomenon is also known as Schulze-Hardy Rule.

Finally, it will a component adjustment (microparticle concentration, water content concentration, etc.) etc. of the dispersion of gold-containing noble metal microparticles by concentration and dehydration, adding an organic solvent etc. performed, so that the coating solution of the present invention, which contains gold Precious metal microparticles (gold-coated silver microparticles) includes.

Moreover, the following method (first production method) can be used to form the transparent two-layered film consisting of a transparent conductive layer and a transparent coating layer of a transparent substrate:
That is, a coating liquid for forming a transparent conductive layer whose main components are a solvent and gold microparticles or gold-containing noble metal microparticles having an average particle diameter of 1 to 100 nm dispersed in this solvent is coated on a transparent substrate (this substrate comprises for example, the front panel of CRTs and PDPs) such as a glass substrate or plastic substrate, etc. by a method such as spray coating, spin coating, wire bar coating, doctor blade coating, gravure coating, roll coating, etc., and drying if necessary. Then, a coating liquid for forming a transparent coating layer whose main components are selected is a functional group-containing compound having at least one functional group selected from mercapto groups (-SH), sulfide groups (-S-) and polysulfide groups (-S _x -, X ≥ 2) and binders such as silica sol, etc., and solvent are coated thereover by the aforementioned means.

When next will after overcoating a heat treatment at a temperature of, for example, 50 to 350 ° C, to the coating liquid for forming a transparent coating layer to harden, the above was coated, and the aforementioned transparent two-layered To make film.

With the aid of this first manufacturing method, the above coated silica sol seeps into the holes in the network structure of the layer of gold microparticles or gold-containing noble metal microparticles which has been passed through the coating liquid to form a transparent conductive layer whose major components are gold microparticles or gold-containing noble metal microparticles the coating liquid for forming a transparent coating layer whose main components are a functional group-containing compound having at least one functional group selected from mercapto groups (-SH), sulfide groups (-S-) and polysulfide groups (-S _x -, X ≥ 2), and a silica sol and solvent is coated over it by the aforementioned method. The silica sol, by the aforementioned heat treatment, comprises a binder matrix containing as its main component silicon oxide and at least one functional group consisting of Mercapto groups (-SH), sulfide groups (-S-) and polysulfide groups (-S _x -, X ≥ 2). In addition, at the end, the improvement in conductivity, the improvement in film strength, and even further improvement in weatherability are simultaneously completed by the firm bonding between this binder matrix with the substrate and the gold microparticles or gold-containing noble metal microparticles.

Moreover, with respect to the optical constant (n-ik) of the transparent conductive layer, the aforementioned gold microparticles or gold-containing noble metal microparticles are dispersed in a binder matrix containing silica as its main component and at least one functional group selected from mercapto groups ( -SH), sulfide groups (-S-) and polysulfide groups (-S _x -, X ≥ 2) was selected, the refractive index is not so large, but the extinction coefficient is large. Consequently, the reflectance of the transparent two-layered film can be remarkably reduced due to the structure of the transparent two-layered film made of the aforementioned transparent conductive layer and transparent coating layer.

Moreover, with respect to the transmitted light beam profile of the above transparent two-layer film, for example, the standard deviation of transmittance of the transparent two-layer film alone without comprising the transparent substrate is 1 to 2% at each wavelength at 5 nm intervals in the visible light wavelength region (380 to 780 nm) small. An extremely flat permeability profile (see 2 ) is received.

Moreover, when the binder matrix comprises the aforementioned functional groups, the same excellent properties are obtained with respect to the reflection and transmission properties of the aforementioned transparent two-layer film when a binder matrix contains silica as its main component and the functional groups of mercapto groups (-SH) , Sulfide groups (-S-), polysulfide groups (-S _x -, x ≥ 2), etc. as the main component does not include. The reason for this is obvious that there is substantially no change in the optical constants of the binder matrix even when functional groups such as mercapto groups (-SH), sulfide groups (-S-), polysulfide groups (-S _x -, X ≥ 2), etc . are introduced into a binder matrix whose main component is silicon oxide.

The mixing ratio of binder such as silica sol, etc., and functional group-containing compound having at least one functional group selected from mercapto groups (-SH), sulfide groups (-S-) and polysulfide groups (-S _x -, x ≥ 2) is disclosed in the above-mentioned coating liquid for forming a transparent coating layer contains 0.1 to 50 parts by weight, preferably 0.5 to 15 parts by weight, of functional group-containing compound per 100 parts by weight of binder. The effects of the aforementioned functional groups are insufficient if there are less than 0.1 parts by weight of functional group-containing compounds, while if more than 50 parts by weight, there will be a reduction in the strength of the binder matrix itself. Moreover, this requirement is the same when a resin binder or when an inorganic binder is used.

Furthermore For example, the silica sol containing a functional group Contains compound and that in the coating liquid for forming a transparent coating layer used is a polymer, wherein hydrolysis and dehydropolycondensation as a result of the addition of water and an acid catalyst to a functional Group-containing silicon compound (containing functional groups Compound) such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3- (2-acetoxyethylthiopropyl) dimethoxymethylsilane, Bis (triethoxysilylpropyl) tetrasulfane, etc., and orthoalkyl silicate, or a polymer (silica sol) proceeds, with others Hydrolysis and dehydropolycondensation as a result of the addition of Water and an acid catalyst have taken place to a commercial alkyl silicate solution, which polymerized to a tetramer or pentamer and to which the aforementioned functional group-containing silicon compound was added.

Furthermore hydrolyzes the alkoxysilyl group segment of the aforementioned functional Group-containing silicon compound in several hours to several days when added to the silica sol. It however, it is preferable that the aforementioned coating liquid for forming the transparent coating layer is used after this hydrolysis. In addition, if the dehydropolycondensation progresses, the viscosity of the solution increases until eventually cures. Consequently, the degree of dehydropolycondensation with respect to the viscosity set to no more than the upper limit with which the coating on a transparent substrate such as a glass substrate or plastic substrate etc. possible is. However, there are no special restrictions on the degree of dehydropolycondensation, as long as he is not higher than this level is.

In addition, the alkyl silicate hydrolysis polymer comprising a functional group-containing compound having at least one functional group selected from mercapto groups (-SH), sulfide groups (-S-) and polysulfide groups (-S _x -, X ≥ 2) is almost completed the dehydro polycondensation when the transparent two-layered film is heated and baked to become a cured silicate film containing as its main component silicon oxide and at least one functional group consisting of mercapto groups (-SH), sulfide groups (-S-) and polysulfide groups ( -S _x -, X ≥ 2) was selected.

In addition, it is possible to adjust the refractive index of the transparent coating layer and to change the reflectance of the transparent two-layered film by adding magnesium fluoride microparticles, alumina sol, titania sol, zirconia sol, etc. to the silica sol which is a functional group-containing compound having at least one functional group which was selected from mercapto groups (-SH), sulfide groups (-S-) and polysulfide groups (-S _x -, X ≥ 2).

Furthermore is it during the method of forming the aforementioned transparent conductive layer just as possible a coating liquid to use for forming a transparent conductive layer which is a mixture of a silica sol as an inorganic binder component, which in addition to the solvent comprising the binder matrix, and gold microparticles or gold-containing Noble metal microparticles having an average particle diameter from 1 to 100 nm dispersed in this solvent. In this case, the coating liquid becomes to form a transparent one conductive layer, which comprises the aforementioned silica sol, applied and dried if necessary. Then the same transparent two-layered Movie through it Coating the aforementioned coating liquid to form a transparent coating layer obtained by the aforementioned methods.

Furthermore can be a coating liquid for forming a transparent conductive layer in which polymer resin was used in the first manufacturing process. If a polymer resin is added, the gold microparticles or Gold-containing noble metal microparticles in the coating liquid stabilized to form a transparent conductive layer and the dripping time of the coating liquid for forming the transparent conductive Layer can be extended. However, there is a tendency toward a slight deterioration the strength and weather resistance of the obtained transparent conductive Film. Consequently, must Precautions are taken when a polymer resin is used.

Next, the transparent conductive layer structure of the present invention can also be obtained by the following second production method:
That is, a coating liquid for forming a transparent conductive layer whose main components are a solvent and gold microparticles or gold-containing noble metal microparticles having an average particle diameter of 1 to 100 nm and a functional group-containing compound having at least one functional group selected from mercapto groups (-SH ), Sulfide groups (-S-) and polysulfide groups (-S _x -, X ≥ 2) and dispersed in this solvent is applied to a transparent substrate (this substrate includes, for example, the front panel of CRTs and PDPs) such as a glass substrate or plastic substrate, etc. are applied by a method such as spray coating, spin coating, wire bar coating, doctor blade coating, gravure coating, roll coating, etc., and dried if necessary. Then, a coating liquid for forming a transparent coating layer whose main components are a binder such as silica sol, etc., and a solvent is coated thereover by the above-mentioned means.

When next will after overcoating a heat treatment at a temperature of, for example, 50 to 350 ° C, to the coating liquid for forming a transparent coating layer to harden, the above was coated, and the aforementioned transparent two-layered To make film.

By means of this manufacturing method, as well as the first manufacturing method, the aforementioned binder such as silica sol, etc., coated over it, seeps into the holes in the network structure of the gold microparticles or gold-containing noble metal microparticles passing through the coating liquid to form a transparent conductive layer Whose main components are gold microparticles or gold-containing noble metal microparticles and a functional group-containing compound have been carried out when the coating liquid is coated thereover to form a transparent coating layer. This silica sol becomes, with the aforementioned heat treatment, a binder matrix containing as its main component silicon oxide and comprising at least one functional group, selected from mercapto groups (-SH), sulfide groups (-S-) and polysulfide groups (-S _x -, x ≥ 2). Moreover, it has been confirmed by the observations of the inventors that the ratio of the binder seeped into the holes of the aforementioned network structure and the functional group-containing compound in the network structure is approximately the same as the ratio of binder and functional in the end Group-containing compound in the coating liquid for forming a transparent coating layer in the first production process.

In addition, the coating liquid for forming a transparent conductive layer of the present invention used in the aforementioned second production method can be produced, for example, by the following method:
That is, a colloidal dispersion of silver microparticles is prepared by the aforementioned method (for example, the Carey-Lea method, Am J. Sci., 37, 47 (1889), Am J. Sci., 38 (1889) For example, a colloidal dispersion of silver microparticles (Ag: 0.1 to 10 wt%) can be easily prepared by adding and reacting a mixture of an aqueous ferrous sulfate solution and an aqueous sodium citrate solution with an aqueous silver nitrate solution. Solution, filtering and washing the precipitate and then adding pure water.

Next, a reducing agent such as hydrazine, etc. is added to the obtained colloidal dispersion of silver microparticles. Further, a mixture of an aurate solution and a functional group-containing compound having at least one functional group selected from mercapto groups (-SH), sulfide groups (-S-) and polysulfide groups (-S _x -, X ≥ 2) [for example, γ Mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3- (2-acetoxyethylthiopropyl) dimethoxymethylsilane, bis (triethoxysilylpropyl) tetrasulfane, thiomalic acid, thiosalicylic acid, thiodiglycolic acid, etc.]. As a result, a colloidal dispersion in which gold-containing noble metal microparticles (gold-coated silver microparticles) and a functional group-containing compound are dispersed can be obtained.

Moreover, with respect to the timing for adding the functional group-containing compound to the aforementioned colloidal dispersion of silver microparticles, the aforementioned compound may be added at a time other than that of the coating, whereby the aforementioned compound is added simultaneously with the aurate solution. It may be added after the coating treatment, wherein the surface of the silver microparticles is coated with gold. However, the functional group-containing compound having at least one functional group selected from mercapto groups (-SH), sulfide groups (-S-) and polysulfide groups (-S _x -, X ≥ 2) should not be included in the colloidal dispersion of silver microparticles alone be mixed before the coating treatment is carried out with gold. This is because, when the above-mentioned compound alone is blended, sufficient coating can not be realized by subsequently performing the gold plating treatment. A dispersion of silver microparticles coated well with gold can not be obtained. The reason for this is obvious that the surface of the silver microparticles is coated by the aforementioned compound with mercapto groups (-SH), sulfide groups (-S-) and polysulfide groups (-S _x -, X ≥ 2) when the aforementioned compound alone was mixed.

When next the electrolyte concentration of the colloidal dispersion, in which gold-containing noble metal microparticles (gold coated Silver microparticles) and a functional group-containing compound dispersed by a process of desalting treatment, such as dialysis, electrodialysis, ion exchange, ultrafiltration etc. be reduced. This is because the colloid is generally associated with the electrolyte will aggregate when the electrolyte concentration not reduced as in the first manufacturing process.

Then, the colloidal dispersion of gold-containing noble metal microparticles (gold-coated silver microparticles) subjected to the aforementioned desalting treatment is concentrated by a reduced-pressure evaporator or a method such as ultrafiltration, etc. to obtain a concentrated dispersion of a functional group-containing compound having mercapto groups (-SH), sulfide groups (-S-) and polysulfide groups (-S _x -, X ≥ 2) and gold-containing noble metal microparticles (gold-coated silver microparticles) to obtain. The coating liquid for forming the transparent conductive layer of the present invention used in the second production method can then be obtained by mixing solvent alone or binder-containing solvent with this concentrated dispersion and performing the adjustment of components (microparticle concentration, water content concentration, etc.) become.

This transparent conductive layer structure of the present invention has a transparent conductive capable layer whose main components are gold microparticles or gold-containing noble metal microparticles having an average particle diameter of 1 to 100 nm and a binder matrix comprising at least one functional group consisting of mercapto groups (-SH), sulfide groups (-S-) and polysulfide groups (- S _x -, X ≥ 2) was selected. As a result, it has excellent film strength and weather resistance when compared with the transparent conductive layer of conventional transparent conductive base materials. It has good conductivity and excellent antireflection effects and a permeability profile.

Consequently, Is it possible, this layer for the front panel etc. of advertisements such as CRTs, PDPs, fluorescent display tubes (VFDs) Field Emission Indicators (FEDs), Electroluminescent Displays (ELDs), liquid crystal displays (LCDs), etc. to use.

Moreover, the coating liquid for forming a transparent coating layer used in the first production method contains as its main components a solvent, a binder and a functional group-containing compound having at least one functional group selected from mercapto groups (-SH), sulfide groups ( -S-) and polysulfide groups (-S _x -, X ≥ 2). The mixing ratio of the binder and the above-mentioned functional group-containing compound is set to 0.1 to 50 parts by weight of the functional group-containing compound per 100 parts by weight of the binder. As a result, it is possible to obtain a transparent conductive layer structure excellent in film strength and weather resistance as compared with transparent conductive layer structures using conventional coating liquids for forming transparent coating layers.

Moreover, the coating liquid for forming a transparent conductive layer used in the second production method contains as its main components a solvent and gold microparticles or gold-containing noble metal microparticles containing 5% by weight or more of gold having an average particle diameter of 1 to 100 nm, and a functional group-containing compound having at least one functional group selected from mercapto groups (-SH), sulfide groups (-S-) and polysulfide groups (-S _x -, X ≥ 2) dispersing in this solvent are. As a result, it is possible to obtain a transparent conductive layered structure having a transparent conductive layer having excellent film strength and weatherability as compared with transparent conductive layered structures using conventional coating liquids for forming transparent conductive layers.

Examples The present invention will be described below with specific reference described. However, the present invention is not limited to these Limited examples. About that In addition, "%" in the text Exception of permeability, the reflection and the turbidity value (%) to "wt%." In addition "parts" refers to "parts by weight".

[Example 1]

A Colloidal dispersion of silver microparticles was through the previously made Carey Lea process. In particular, it was after adding a mixture of 39 g of aqueous 23% ferrous sulfate solution and 48 g of aqueous 37.5% sodium citrate solution to 33 g of aq 9% silver nitrate solution the precipitate filtered and washed. Then it became pure water added to a colloidal dispersion of silver microparticles (Ag: 0.15%).

Next, 0.8 g of aqueous 1% hydrazine monohydrate solution (N ₂ H ₄ .H ₂ O) and a mixture of 480 g of aqueous potassium aaurate solution [KAu (OH) ₄ ] (Au: 0.075%) and O Add 2 g of 1% polymeric dispersant solution to 60 g of this colloidal dispersion of silver microparticles while stirring to give a colloidal dispersion of gold-coated silver microparticles (gold-containing noble metal microparticles).

A Desalting of this colloidal dispersion of gold coated Silver microparticles (gold-containing noble metal microparticles) was reacted with an ion exchange resin (Diaion SK1B, SA20AP; by Mitsubishi Chemical Corporation). The product was through Ultrafiltration on concentrated. Ethanol (EA) and diacetone alcohol (DAA) were added to a coating solution to form a transparent conductive Layer (Ag: 0.08%, Au: 0.32%, water: 10.7%, EA: 83.9%, DAA: 5.0%).

As a result of observation of the obtained coating liquid to form a transparency In the case of the conductive layer under a transmission electron microscope, the average particle diameter of the gold-coated silver microparticles (gold-containing noble metal microparticles) was 5.8 nm.

When next became the coating liquid for forming a transparent conductive layer on a glass substrate (Soda-lime glass with a thickness of 3 mm) (150 rev / min, 120 seconds), that at 35 ° C had been heated, spin-coated. The coating liquid for forming a transparent coating layer, which will be discussed below was then spin-coated (150 rpm, 60 seconds) and the product also for 20 minutes at 180 ° C hardened, around a glass substrate with a transparent two-layer film obtained from a transparent conductive layer gold-containing noble metal microparticles and a mercapto group comprehensive binder matrix and a transparent coating layer, which was composed of a silicate film, as its Main component containing silica and mercapto groups exists. This means, the transparent conductive Layer structure of Example 1 was obtained.

Furthermore is there a possibility formation of an alloy layer as a result of heat diffusion of Gold and Silver of Gold Coated Silver Microparticles, if the aforementioned heat treatment for 20 Minutes at 180 ° C carried out becomes. There are cases in which the coating layers of aforementioned gold-coated silver microparticles are not sufficient Gold are made alone. Consequently, in the present Specification the microparticles, which gold and silver in the transparent conductive Layer of a finished transparent conductive layer structure include, not as gold-coated silver particles, but rather represented as gold and silver bicomponent microparticles (gold-containing Noble metal microparticles) as previously noted when gold coated Silver microparticles in the coating liquid to form a transparent conductive Layer can be used.

The silica sol comprising a functional group-containing compound constituting the aforementioned coating liquid for forming a transparent coating layer is used herein by preparing a substance having a SiO ₂ (silica) solid content concentration of 10% and a weight-average molecular weight of 2.070 of 7.4 parts of methyl silicate 51 (Colcoat Co., trade name), 3.6 lines of γ-mercaptopropyltrimethoxysilane, 56.3 parts of ethanol, 7.9 parts of aqueous 1% nitric acid solution and 14.7 parts of pure water, and then diluting the same a mixture of isopropyl alcohol (IPA) and n-butanol (NBA) (IPA / NBA = 3/1) to a final SiO ₂ solids content concentration of 0.8%.

Furthermore become the film properties of the transparent two-layer film, which was formed on the glass substrate (surface resistance, permeability for visible Light rays, standard deviation of permeability, haze value, Ground reflection / fundamental wavelength) shown in Table 1b.

Furthermore The above basic reflection means the minimum reflectance in the Reflection profile of the transparent conductive layer structure. Fundamental wavelength means the wavelength, when the reflection is at its minimum.

In addition, the reflection profile of the prepared transparent conductive layer structure of Example 1 in 1 while the transmission profiles, which were determined inclusive for each substrate, are shown together in FIG 2 to be shown.

Moreover, the transmittance of the transparent two-layer film alone, without including the transparent substrate (glass substrate), is found at each wavelength at 5 nm intervals of the visible light beam wavelength range (380 to 780 nm) in Table 1b as follows: That is, Transmittance of the transparent two-layered film only without transparent substrate (%) = [(transmittance determined inclusive of the transparent substrate) / (transmittance of the transparent substrate)] × 100

If not otherwise noted here in the present specification the permeability of the transparent two-layer film alone, without the transparent one To include substrate, as a transmittance used.

Furthermore became the surface resistance of the transparent two-layer film using the surface resistance measuring device Loresta AP (MCP-T400) from Mitsubishi Chemical Corporation.

Of the haze value and the transmittance for visible Light rays were measured using a turbidity meter (HR-200), manufactured by Murakami Color Research Laboratory, determined.

Of the Reflectance and reflection transmission profiles were under Using a spectrophotometer (U-4000) manufactured by Hitachi Ltd., certainly. additionally became the particle diameter of the gold-containing noble metal microparticles under a transmission electron microscope, manufactured by JEOL Ltd., evaluated.

[Example 2]

Except the Fact that a silica sol with a weight average Molecular weight of 2.460, which contains a functional group Compound comprised of 19.0 parts of methyl silicate 51 (Colcoat Co., trade name), 1.0 part of γ-mercaptopropyltrimethoxysilane, 57.4 parts of ethanol, 7.9 parts of aqueous 1% nitric acid solution and 14.7 parts of pure water during the preparation of the coating liquid for forming a transparent coating layer was obtained, a glass substrate with a transparent two-layered Film obtained from the transparent conductive layer gold-containing noble metal microparticles and a mercapto group comprehensive binder matrix and a transparent coating layer, which was composed of a silicate film containing when its main components contained silica and mercapto groups, consists. This means, the transparent conductive Layer structure of Example 2 was in the same manner as obtained in Example 1. The film properties of the transparent two-layered film formed on the glass substrate are shown in Table 1b below.

[Example 3]

Except for the fact that a coating liquid for forming the transparent conductive layer, which silica binders (Ag: 0.08%, Au: 0.32%, SiO ₂ : 0.02%, water: 10.7%, EA: 83, 8%, DAA: 5.0%) by adding the below-described silica sol during the solvent-diluting process to prepare a coating liquid for forming a transparent conductive layer in Example 1, a glass substrate having a transparent two-layered film was obtained transparent conductive layer of gold-containing noble metal microparticles and a binder matrix comprising mercapto groups and a transparent coating layer composed of a silicate film containing as its main component silica and mercapto groups. That is, the transparent conductive layer structure of Example 3 was obtained in the same manner as in Example 1. The film properties of the transparent two-layered film formed on the glass substrate are shown in Table 1b below.

In addition, the silica sol added during the aforementioned solvent dilution process was prepared by preparing a substance having a SiO ₂ (silica) solid content concentration of 10% and a weight-average molecular weight of 4.95 mol, using 19.6 parts Methyl silicate 51 (Colcoat Co., trade name), 57.8 parts ethanol, 7.9 parts aqueous 1% nitric acid solution and 14.7 parts pure water and then desalting it with an ion exchange resin (Diaion SK1B, SA20AP, trade name of Mitsubishi Chemical Corporation ) receive.

[Example 4]

Except the Fact that a coating liquid for forming a transparent coating layer by adding 0.016 part of γ-mercaptopropyltrimethoxysilane to 100 parts of the silica sol described below became a glass substrate with a transparent two-layered film obtained from a transparent conductive layer of gold containing Noble metal microparticles and a binder matrix comprising mercapto groups and a transparent coating layer, which was composed of a silicate film, as its main components Silica and mercapto groups exists. That is, the transparent conductive Layer structure of Example 4 was in the same manner as obtained in Example 1. The film properties of the transparent two-layered film formed on the glass substrate are shown in Table 1b below.

The aforementioned silica sol is prepared by preparing a substance having a SiO ₂ (silica) solid content concentration of 10% and a weight average molecular weight of 1.190 using 19.6 parts of methyl silicate 51 (Colcoat Co., trade name), 57.8 parts of ethanol, 7 , 9 parts of aqueous 1% nitric acid solution and 14.7 parts of pure water and then diluting it with a Mi isopropyl alcohol (IPA) and n-butanol (NBA) (IPA / NBA = 3/1) to a final SiO ₂ solids content concentration of 0.8%.

[Example 5]

Except the Fact that a coating liquid for forming a transparent conductive layer (Ag: 0.13%, Au: 0.27%, water: 10.7%, EA: 83.9%, DAA: 5.0%) Vary the conditions of mixing the starting materials in the Method of producing a colloidal dispersion of gold coated silver microparticles (gold-containing noble metal microparticles) in Example 1, a glass substrate having a transparent one was obtained obtained two-layer film, which consists of a transparent conductive layer gold-containing noble metal microparticles and a mercapto group comprehensive binder matrix and a transparent conductive layer, which was composed of a silicate film, as its Main components containing silica and mercapto groups exists. This means, the transparent conductive Layer structure of Example 5 was in the same manner as obtained in Example 4. The film properties of the transparent two-layered film formed on the glass substrate are shown in Table 1b below.

[Example 6]

Except the Fact that a coating liquid for forming a transparent coating layer by adding 0.004 part of γ-mercaptopropyltrimethoxysilane to 100 parts of the silica sol, a glass substrate was obtained obtained with a transparent two-layer film, which consists of a transparent conductive Layer of gold-containing noble metal microparticles and a Mercapto groups comprising binder matrix and a transparent coating layer, which was composed of a silicate film, as its Main components containing silica and mercapto groups exists. The is called, the transparent conductive Layer structure of Example 6 was in the same manner as obtained in Example 4. The film properties of the transparent two-layered film formed on the glass substrate are shown in Table 1b below.

[Example 7]

Except the Fact that 0.01 part of acrylic polymer resin is 100 parts of the coating liquid for forming a transparent conductive layer of example 1 was added, a glass substrate with a transparent two-layer film obtained from a transparent conductive layer gold-containing noble metal microparticles, a polymer resin and a binder matrix comprising mercapto groups and a transparent coating layer, which was composed of a silicate film, as its main components Silica and mercapto groups exists. That is, the transparent conductive layer structure from Example 7 was prepared in the same manner as in Example 4 received. The film features of the transparent two-layer Films formed on the glass substrate are tabulated 1b shown below.

[Example 8]

Except the Fact that a coating liquid for forming a transparent coating layer by adding 0.016 part of γ-mercaptopropylmethyldimethoxysilane to 100 parts of the silica sol of Example 4 was obtained, a glass substrate with a transparent two-layer film was obtained, which consists of a transparent conductive layer of gold Noble metal microparticles, a polymer resin and a mercapto group comprehensive binder matrix and a transparent coating layer, which was composed of a silicate film, as its Main components containing silica and mercapto groups exists. This means, the transparent conductive Layer structure of Example 8 was in the same manner as obtained in Example 7. The film features of the transparent two-layer Films formed on the glass substrate are tabulated 1b shown below.

[Example 9]

Except for the fact that a coating liquid for forming a transparent coating layer was obtained by adding 0.016 part of 3- (2-acetoxyethylthiopropyl) dimethoxymethylsilane to 100 parts of the silica sol in Example 4, there was obtained a glass substrate having a transparent two-layered film consisting of a transparent one conductive layer of gold-containing noble metal microparticle and a transparent coating layer composed of a silicate film containing as its main components silica and sulfide groups. That is, the transparent conductive layer structure of Example 9 was obtained in the same manner as in Example 7. The film properties of the transparent two-layered film formed on the glass substrate are shown in Table 1b below.

[Example 10]

Except the Fact that a coating liquid for forming a transparent coating layer by adding 0.016 part of bis (triethoxysilylpropyl) tetrasulfan to 100 parts of the silica sol of Example 4 was obtained, was a glass substrate with a transparent two-layer film obtained from a transparent conductive layer of gold containing Noble metal microparticles and a polysulfide group comprising Binder matrix and a transparent coating layer, which consists of a silicate film composed as its main components Silica and polysulfide groups exists. That is, the transparent conductive Layer structure of Example 10 was in the same manner as obtained in Example 7. The film properties of the transparent two-layered film formed on the glass substrate are shown in Table 1b below.

[Example 11]

Except the Fact that a coating liquid for forming a transparent conductive film (Ag: 0.24%, Au: 0.96%, water: 16.0%, EA: 72.8%, NBA: 5.0%, DAA: 5.0%) by adding ethanol (EA), 1-butanol (NBA) and diacetone alcohol (DAA) to a concentrated liquid the colloidal dispersion of gold coated silver microparticles (Gold-containing noble metal microparticles) obtained in Example 1 and this coating liquid for forming a transparent conductive layer on a Heated to 40 ° C Glass substrate was spin-coated (120 rpm, 120 seconds), was a glass substrate with a transparent two-layer film obtained from a transparent conductive layer of gold containing Noble metal microparticles and a binder matrix containing mercapto groups and a transparent coating layer, which was composed of a silicate film, as its Main components containing silica and mercapto groups exists. This means, the transparent conductive Layer structure of Example 11 was in the same manner as obtained in Example 6. The film properties of the transparent two-layered film formed on the glass substrate are shown in Table 1b below.

Comparative Example 1

Except the Fact that the silica sol described below as Coating liquid for Forming a transparent coating film from Example 1 was used, a glass substrate with a transparent two-layer film obtained from a transparent conductive Layer of gold-containing noble metal microparticles and a Binder matrix of silica and a transparent coating layer, which was composed of a silicate film, as its Main component containing silica exists. That is, the transparent conductive Layer structure of Comparative Example 1 was in the same way and manner as in Example 1. The film properties of the transparent two-layer film, which is on the glass substrate are shown in Table 1b below.

The aforementioned silica sol was prepared by preparing a substance having a SiO ₂ (silica) solid content concentration of 10% and a weight average molecular weight of 1.920 using 19.6 parts of methyl silicate 51 (Colcoat Co., trade name), 57.8 parts of ethanol , 7.9 parts aqueous 1% sulfuric acid solution and 14.7 parts pure water and then diluting them with a mixture of isopropyl alcohol (IPA) and n-butanol (NBA) (IPA / NBA = 3/1) on a final SiO ₂ Fixed content concentration of 0.8%.

Comparative Example 2

Anmerkung 1:

R ist eine Methylgruppe oder Ethylgruppe.

Anmerkung 2:

Gewichtsteile der funktionelle Gruppen enthaltenden Verbindung/Gewichtsteile Siliciumoxidbinder.

Tabelle 1b

Anmerkung 3:

Wert des Durchlässigkeitsgrades (%) des transparenten zweischichtigen Films alleine, ohne das transparente Substrat zu umfassen, bei jeder Wellenlänge in 5 nm Intervallen in dem sichtbaren Lichtwellenlängenbereich (380 bis 780 nm).

In addition to the fact that the silica sol in Example 4 was used as a coating liquid for forming a transparent coating layer, there was obtained a glass substrate having a transparent two-layered film consisting of a transparent conductive layer of gold-containing noble metal microparticles, a polymer resin and a binder matrix of silica transparent coating layer composed of a silicate film containing as its main component silica. That is, the transparent conductive layer structure of Comparative Example 2 was in the same chen way as obtained in Example 7. The film properties of the transparent two-layered film formed on the glass substrate are shown in Table 1b below. Table 1a

Note 1:

R is a methyl group or ethyl group.

Note 2:

Parts by weight of the functional group-containing compound / parts by weight of silica binder.

Table 1b

Note 3:

Value of transmittance (%) of the transparent two-layer film alone, without including the transparent substrate, at each wavelength at 5 nm intervals in the visible light wavelength range (380 to 780 nm).

Weather resistance test 1]

The transparent conductive Layer structures of Examples 1 to 3 and the transparent conductive layer structure of Comparative Example 1 were for 3 months under condition of exposure to direct Sunlight and rain placed outdoors and then the surface resistance and the external appearance the film of the transparent two-layered film on the transparent Substrate (glass substrate) checked. The Results are shown in Table 2.

Table 2

[Weather resistance test 2]

The transparent conductive layer structures of Examples 4 to 11 and the transparent conductive layer structure of Comparative Example 2 were evaluated for their surface resistance and the external appearance of the film of the transparent two-layered film formed on the transparent substrate using an ultraviolet irradiation accelerated tester (Eye Super UV Tester, SUV-W131, Iwasaki Electric Co., Ltd., ultraviolet irradiation intensity: 100 mW / cm ² ). The results are shown in Table 3.

Table 3

[Film strength tests]

O:

keine Kratzer,

Δ:

einige Kratzer, und

X:

viele Kratzer.

Rubber eraser tests (the film surface was continuously rubbed back and forth 50 times and 100 times with a rubber eraser under a load of 1 kg and then examined for scratches) were made on the transparent conductive layer structures of Examples 1 to 3 and the transparent conductive layer structure of Comparative Example 1 and then checking the film strength of the transparent two-layered film on the transparent substrate (glass substrate). The results are shown in Table 4. The evaluation criteria in Table 4 are

O:

no scratch,

Δ:

some scratches, and

X:

many scratches.

Table 4

[Evaluation Criteria]

• O:

  no scratch,

  Δ:

  some scratches, and

  X:

  many scratches.

[Evaluation]

• 1. As is clear from the results in Table 1b, the values of the surface resistivity (Ω / □) and the standard deviation of the transmittance of the transparent two-layered film of each example are similarly much better in properties than the values of the transparent two-layered film each comparative example. As well as from the transmission profile of the transparent conductive layer structure of Example 1, which in 2 As can be seen, it has also been confirmed that a very flat transmission profile is obtained with the transparent conductive layer structure of Example 1. As further from the reflection profile in 1 becomes clear, it has also been confirmed that the transparent conductive layer structure of Example 1 has excellent reflection properties in the visible light wavelength region.
• 2. As additional from the results shown in Tables 2 and 3 contrary to the fact that the surface resistance the transparent two-layer films of Comparative Examples 1 and 2 changes, approved was that weather resistance of the transparent two-layer films in each example with nearly no change of surface resistance of the transparent two-layer film remarkably improved has been.
• 3. How about it In addition, as is clear from the results in Table 4, it was confirmed that the strength of the transparent two-layer film in Examples 1 to 3 compared to the transparent two-layered film in FIG Comparative Example 1 is improved.
• 4. Otherwise were gold and silver bicomponent microparticles (Gold-containing noble metal microparticles) as metal microparticles used in each example and comparative example. But exams were also using gold microparticles at the site of Gold-containing noble metal microparticles carried out, and it has been confirmed, that the same evaluation as in each example is obtained when gold microparticles are used as metal microparticles.

[Example 12]

A colloidal dispersion of silver microparticles was prepared by the aforementioned Carey Lea method. Specifically, after adding a mixture of 39 g of aqueous 23% ferrous sulfate solution and 48 g of aqueous 37.5% sodium citrate solution to 33 g of aqueous 9% silver nitrate solution, the precipitate was filtered and washed. Then, pure water was added to prepare a colloidal dispersion of silver microparticles (Ag: 0.15%). Next, 10.0 g of a 1% hydrazine monohydrate aqueous solution (N ₂ H ₄ .H ₂ O) was added to 80 g of this colloidal dispersion of silver microparticles. A mixture of 320 g of aqueous potassium aurate solution [KAu (OH) ₄ ] (Au: 0.15%) and 0.6 g of aqueous 1% thiomalic acid solution were added with stirring to give a colloidal dispersion of thiomalic acid and gold coated silver microparticles (gold-containing noble metal microparticles).

After this single desalting of this colloidal dispersion of thiomalic acid and Gold coated silver microparticles (gold coated noble metal microparticles) with an ion exchange resin (Diaion SK1B, SA20AP; Mitsubishi Chemical Corp.), the product was passed through Ultrafiltration on concentrated. Ethanol (EA) and diacetone alcohol (DAA) were added to a coating liquid to form a transparent conductive Layer (Ag: 0.06%, Au: 0.25%, thiomalic acid: 0.003%, water: 9.7%, DAA: 10.0%, EA: 79.9%). As a result of observation the coating liquid for forming a transparent conductive layer underlying a Transmission electron microscope was obtained, the average particle diameter of the gold coated Silver microparticles (gold-containing noble metal microparticles) 7,8 nm.

When next became the coating liquid for forming a transparent conductive layer on a glass substrate (Soda-lime glass with a thickness of 3 mm) heated to 35 ° C was spin-coated (150 rpm, 60 seconds). A coating liquid for forming a transparent coating layer, which consisted of a silica sol was then spin-coated (150 rpm, 60 seconds) and the product also for 20 minutes at 200 ° C hardened, around a glass substrate with a transparent two-layer film obtained from a transparent conductive layer of a gold and silver bicomponent microparticle (gold-containing noble metal microparticles) and a binder matrix comprising mercapto groups and a transparent coating layer, which was composed of a silicate film, as its Main component containing silica exists. That is, the transparent conductive Layer structure of Example 12 was obtained.

The aforementioned silica sol was prepared by preparing a substance having a SiO ₂ (silica) solid content concentration of 10% and a weight average molecular weight of 2,850 using 19.6 parts of methyl silicate 51 (Colcoat Co., trade name), 57.8 parts of ethanol , 7.9 parts aqueous 1% nitric acid solution and 14.7 parts pure water and then diluting it with a mixture of isopropyl alcohol (IPA) and n-butanol (NBA) (IPA / NBA = 3/1) to a final SiO ₂ solids content concentration of 0.8%.

Furthermore were the film properties of the transparent two-layer film, which had been formed on the glass substrate (surface resistance, Transmittance visible light rays, standard deviation of transmittance, Haze value, Basic reflectance / fundamental wavelength) shown in Table 5b.

In addition, the reflection profile of the prepared transparent conductive layered structure of Example 12 becomes 3 while the permeability profile in 4 will be shown.

[Example 13]

Ethanol (EA), diacetone alcohol (DAA) and a tetramer of tetramethylsilicate (Methylsilicate 51, trade name of Colcoat Co., Ltd.) as an inorganic binder were added to a concentrated liquid of the colloidal dispersion in which thiomalic acid and gold-coated silver microparticles (gold-containing Noble metal microparticles) prepared in Example 12 to obtain a coating liquid for forming a transparent conductive layer comprising thiomalic acid and gold-coated silver microparticles (gold-containing noble metal microparticles) having an average particle diameter of 7.8 nm (Ag: O) , 06%, Au: 0.25%, thiomalic acid: 0.003%, SiO ₂ : 0.01%, water: 9.7%, DAA: 10.0%, EA: 79.9%).

Except the Fact that this coating liquid to form a transparent conductive layer was then used a glass substrate with a transparent obtained two-layer film, which consists of a transparent conductive layer gold and silver bicomponent microparticles (gold-containing precious metal particles) and a binder matrix comprising mercapto groups and a transparent coating layer, which was composed of a silicate film, as its Main component containing silica exists. That is, the transparent conductive Layer structure of Example 13 was in the same manner as obtained in Example 12.

The Film properties of the transparent two-layer film, which on the glass substrate are shown in Table 5b below shown.

[Example 14]

The same treatment as in Example 12 was carried out using 80 g of the colloidal dispersion of silver microparticles prepared by the same method as in Example 12 and 7.0 g of an aqueous 1% solution of hydrazine monohyrate (N ₂ H ₄ . H ₂ O), 240 g of an aqueous solution of potassium aurate [KAu (OH) ₄ ] (Au: 0.15%) and 0.16 g of an aqueous 1% solution of sodium thiosalicylate, to give a coating liquid for forming a transparent conductive layer comprising thiosalicylic acid and gold-coated silver microparticles (gold-containing noble metal microparticles) having an average particle diameter of 9.1 nm (Ag: 0.08%, Au: 0.22%, thiosalicylic acid: 0.002%, water: 12, 1%, DAA: 10.0%, EA: 77.4%).

Except the Fact that this coating liquid to form a transparent conductive layer was then a glass substrate with a transparent obtained two-layer film, which consists of a transparent conductive layer of gold and silver bicomponent microparticles (gold-containing noble metal microparticles) and a binder comprising mercapto groups and a transparent coating layer, which was composed of a silicate film, as its Main component containing silica exists. That is, the transparent conductive Layer structure of Example 14 was in the same manner as obtained in Example 12.

The Film properties of the transparent two-layer film, which on the glass substrate are shown in Table 5b below shown.

[Example 15]

The same treatment as in Example 12 was carried out using 80 g of the colloidal dispersion of silver microparticles prepared by the same method as in Example 12 and 10.0 g of an aqueous 1% solution of hydrazine monohydrate (N ₂ H ₄ H ₂ O), 320 g of an aqueous solution of potassium aurate [KAu (OH) ₄ ] (Au: 0.15%) and 1.2 g of an aqueous 1% solution of thiodiglycolic acid, so that a coating liquid for forming a transparent conductive layer was obtained, which thiodiglycolic acid and gold-coated silver microparticles (gold-containing Edelme tall microparticles) having a mean particle diameter of 8.8 nm (Ag: 0.06%, Au: 0.024%, thiodiglycolic acid: 0.006%, water: 10.2%, DAA: 10.0%, EA: 79.4%. ).

Except the Fact that this coating liquid to form a transparent conductive layer was then used a glass substrate with a transparent obtained two-layer film, which consists of a transparent conductive layer of gold and silver bicomponent microparticles (gold-containing noble metal microparticles) and a binder matrix comprising sulfide groups and a transparent coating layer, which was composed of a silicate film, as its Main component containing silica exists. That is, the transparent conductive Layer structure of Example 15 was in the same manner as obtained in Example 12.

The Film properties of the transparent two-layer film, which on the glass substrate are shown in Table 5b below shown.

[Example 16]

The same treatment as in Example 12 was carried out using 80 g of a colloidal dispersion of silver microparticles prepared by the same method as in Example 12 and 10 g of an aqueous 1% solution of hydrazine monohydrate (N ₂ H ₄ .H ₂ O), 320 g of an aqueous solution of potassium aurate [KAu (OH) ₄ ] (Au: 0.15%) and 0.2 g of an aqueous 1% solution of dithiodiglycolic acid, so that a coating liquid for forming a transparent conductive layer containing dithiodiglycolic acid and gold-coated silver microparticles (gold-containing noble metal microparticles) having an average particle diameter of 7.1 nm (Ag: 0.05%, Au: 0.23%, dithiodiglycolic acid: 0.001%, water: 9.3%). , DAA: 10.0%, EA: 80.3%).

Except the Fact that this coating liquid to form a transparent conductive layer was then used a glass substrate with a transparent obtained two-layer film, which consists of a transparent conductive layer of gold and silver bicomponent microparticles (gold-containing noble metal microparticles) and a disulfide group-containing binder matrix and a transparent coating layer, which was composed of a silicate film, as its Main component containing silica exists. That is, the transparent conductive Layer structure of Example 16 was in the same manner as obtained in Example 12.

The Film properties of the transparent two-layer film, which on the glass substrate are shown in Table 5b below shown.

[Example 17]

The same treatment as in Example 12 was carried out using 80 g of the colloidal dispersion of silver microparticles prepared by the same method as in Example 12 and 10.0 g of an aqueous 1% solution of hydrazine monohydrate (N ₂ H ₄ . H ₂ O), 320 g of an aqueous solution of potassium aurate [KAu (OH) ₄ ] (Au: 0.15%) and 0.6 g of an aqueous 1% solution of γ-mercaptopropyltrimethoxysilane, to prepare a coating liquid a transparent conductive layer was obtained which γ-mercaptopropyltrimethoxysilane (silanol groups [Si-OH] are formed promptly when the methoxy groups in the coating liquid hydrolyze) and gold-coated silver microparticles (gold-containing noble metal microparticles) having an average particle diameter of 8.3 nm ( Ag: 0.06%, Au: 0.23%, γ-mercaptopropyltrimethoxysilane: 0.003%, water: 8.6%, DAA: 10.0%, EA: 81.0%).

Except the Fact that this coating liquid to form a transparent conductive layer was then used a glass substrate with a transparent obtained two-layer film, which consists of a transparent conductive layer of gold and silver bicomponent microparticles (gold-containing noble metal microparticles) and a binder matrix comprising mercapto groups and a transparent coating layer, which was composed of a silicate film, as its main component Silica exists. That is, the transparent conductive layer structure from Example 17 was prepared in the same manner as in Example 12 received.

The Film properties of the transparent two-layer film, which on the glass substrate are shown in Table 5b below shown.

Comparative Example 3

The same treatment as in Example 12 was repeated using 80 g of the colloidal dispersion of silver microparticles prepared by the same method as in Example 12 and 7.0 g of an aqueous 1% solution of hydrazine monohydrate (N ₂ H ₄ . H ₂ O), 240 g of an aqueous solution of potassium aurate [KAu (OH) ₄ ] (Au: 0.15%) and 0.48 g of an aqueous 1% solution of a polymeric dispersant, so that a coating liquid for forming a transparent conductive layer comprising gold-coated silver microparticles (gold-containing noble metal microparticles) having an average particle diameter of 8.3 nm (Ag: 0.08%, Au: 0.23%, water: 12.0%, DAA: 10) , 0%, EA: 77.9%).

Except the Fact that this coating liquid to form a transparent conductive layer was then used a glass substrate with a transparent obtained two-layer film, which consists of a transparent conductive layer of gold and silver bicomponent microparticles (gold-containing noble metal microparticles) and a binder matrix and a transparent coating layer consisting of a silicate film composed as its main component Silica exists. That is, the transparent conductive layer structure from Comparative Example 3 was prepared in the same manner as obtained in Example 12.

Anmerkung 1:

Die funktionelle Gruppe A ist eine funktionelle Gruppe, welche aus Mercaptogruppen (-SH), Sulfidgruppen (-S-) und Polysulfidgruppen (-S_x-, x ≥ 2) ausgewählt wurde.

Anmerkung 2:

Die funktionelle Gruppe B ist eine funktionelle Gruppe, die die funktionelle Gruppen enthaltende Verbindung zusätzlich zu der zuvor genannten funktionellen Gruppe A aufweist.

Tabelle 5b

Anmerkung 3:

Der Wert des Durchlässigkeitsgrads (%) eines transparenten zweischichtigen Films alleine, ohne das transparente Substrat zu umfassen, bei jeder Wellenlänge in 5 nm Intervallen in dem sichtbaren Lichtwellenlängenbereich (380 bis 780 nm)

The film properties of the transparent two-layer film formed on the glass substrate are shown in Table 5b below. Table 5a

Note 1:

The functional group A is a functional group selected from mercapto groups (-SH), sulfide groups (-S-) and polysulfide groups (-S _x -, x ≥ 2).

Note 2:

The functional group B is a functional group having the functional group-containing compound in addition to the aforementioned functional group A.

Table 5b

Note 3:

The value of transmittance (%) of a transparent two-layer film alone, without including the transparent substrate, at each wavelength at 5 nm intervals in the visible light wavelength range (380 to 780 nm)

[Weather resistance test]

The transparent conductive Layer structures of Examples 12 to 17 and the transparent conductive layer structure from Comparative Example 3 were for 3 months under conditions of exposure to direct Sunlight and rain placed outdoors and then the surface resistance and the external appearance the film of the transparent two-layered film on the transparent Substrate (glass substrate) tested. The results are shown in Table 6.

Table 6

[Film strength test]

Rubber eraser tests (the film surface was continuously 50 and 100 times with a Rubber erosion rubber was rubbed forward and backward under a load of 1 kg and then examined for scratches) were performed on the transparent conductive layer patterns of Examples 12 to 17 and the transparent conductive layer structure of Comparative Example 3, and the film strength of the transparent two-layered film on the transparent substrate (glass substrate ) checked.

The Results are shown in Table 7 below.

Table 7

Evaluation criteria:

• O:

  no scratch,

  Δ:

  some scratches, and

  X:

  many scratches.

[Evaluation]

• 1. As is clear from the results in Table 6 there will be no changes the external appearance of the transparent two-layer film of each example, and it There are no big changes of the initial one Value and value after 3 months of standing outdoors in relation on the surface resistance the transparent two-layered film. Consequently, you can approved be that weather resistance of the transparent two-layer film of each example satisfactorily is. On the other hand, though there are no changes in the outward appearance of the transparent two-layered film of the comparative example 3 there was a big change of the initial one Value (2253 Ω / ☐) and the value after 3 months outdoors (5795 (Ω / ☐) in relation to the Surface resistance of the transparent two-layer film, and it can be confirmed that the weather resistance of the transparent two-layered film of the comparative example 3 is insufficient.
• 2. About it In addition, it can be confirmed from the results in Table 7, that the mechanical strength of the transparent two-layered Films of each example compared to Comparative Example 3 sufficient is, and that the mechanical strength of the transparent two-layer Films of each example is sufficient.
• 3. By the way were gold and silver bicomponent microparticles (Gold-containing noble metal microparticles) in each example and Comparative example used as metal microparticles. experiments using gold microparticles instead of this gold containing However, noble metal microparticles were also carried out. Furthermore was confirmed, that the same evaluation as in each example is obtained when gold microparticles are used as metal microparticles.

The present invention relates to a transparent conductive layered structure comprising a transparent substrate, a transparent conductive layer and a transparent coating layer, which are sequentially formed on the substrate in this order. It is used, for example, in front panels of displays such as CRTs, etc. The transparent conductive layer structure according to the invention is characterized in that the main components of the aforementioned transparent conductive layer are gold microparticles or gold-containing noble metal microparticles containing 5% by weight or more of gold having an average particle diameter of 1 to 100 nm and a binder matrix which comprises at least one functional group selected from mercapto groups (-SH), sulfide groups (-S) and polysulfide groups (-S _x , x ≥ 2). The film strength and weatherability of the transparent conductive layer are improved because the noble metal microparticles and a binder matrix over the above mentioned functional groups are firmly connected.

Claims (21)

Transparent conductive layer structure comprising a transparent substrate, a transparent conductive layer and a transparent coating layer, the transparent conductive layer and the transparent coating layer are successively formed in this order on the transparent substrate, the transparent conductive layer structure being characterized in that the main components of the transparent conductive layer are gold microparticles or gold-containing noble metal microparticles containing 5% by weight or more of gold having a mean particle diameter of 1 to 100 nm and a binder matrix comprising at least one functional group selected from mercapto-SH, sulfide groups -S and polysulfide -S _x - was selected, wherein X ≥ 2. The transparent conductive layer structure according to claim 1, wherein the gold content in the gold-containing noble metal microparticles is set in a range of 50 to 95% by weight. The transparent conductive layer structure according to claim 1, wherein the gold-containing noble metal microparticles gold and silver microparticles of a two-component type. The transparent conductive layer structure according to claim 1, wherein the main component of the binder matrix of the transparent conductive Layer is silicon oxide. The transparent conductive layered structure according to claim 1, wherein the transparent coating layer has as its main component silicon oxide and comprises at least one functional group selected from mercapto groups -SH, sulfide groups -S-, and polysulfide groups -S _x - has been chosen, wherein X ≥ 2. The transparent conductive layer structure according to claim 1, wherein the transparent conductive Layer a surface resistance from 5 to 3000 Ω / □, and wherein a standard deviation of the optical transmission of a transparent two-layer film, which is the transparent substrate does not include and from the transparent conductive Layer and the transparent coating layer exists, at every wavelength at 5 nm intervals in a visible light beam wavelength range (380 to 780 nm) is 0 to 5%. A process for producing a transparent conductive layered structure having a transparent substrate, a transparent conductive layer and a transparent coating layer, the transparent conductive layer and the transparent coating layer are sequentially formed in this order on the transparent substrate, the method comprising the steps of: applying a coating liquid to Forming a transparent conductive layer on a transparent substrate, the main components of the coating liquid are a solvent and gold microparticles or gold-containing noble metal microparticles containing 5% by weight or more of gold having an average particle diameter of 1 to 100 nm, and those disclosed in U.S. Pat be dispersed in the solvent; thereafter applying a coating liquid for forming a transparent coating layer whose main components are a binder, a solvent and a functional group-containing compound having at least one functional group selected from mercapto groups -SH, sulfide groups -S- and polysulfide groups -S _x - where X ≥ 2; and performing a heat treatment. A process for producing a transparent conductive layered structure having a transparent substrate, a transparent conductive layer and a transparent coating layer, the transparent conductive layer and the transparent coating layer are successively formed in this order on the transparent substrate, the method comprising the steps of: applying a coating liquid to Forming a transparent conductive layer on a transparent substrate, the main components of the coating liquid are a solvent, gold microparticles or gold-containing noble metal microparticles containing 5% by weight or more of gold having an average particle diameter of 1 to 100 nm, and in that Solvent dispersed, and a functional group-containing compound having at least one functional group selected from mercapto groups -SH, sulfide groups -S- and polysulfide groups -S _x - where when X is ≥ 2; then applying a coating liquid to form a transparent coating layer whose main components are a binder and a solvent; and performing a heat treatment. A method of producing a transparent conductive Layer structure according to claim 7 or 8, wherein the gold content of the gold-containing noble metal microparticles in a range of 50 to 95 wt .-% is set. A method of producing a transparent conductive A layered structure according to claim 7 or 8, wherein the gold-containing Precious metal microparticles are gold-coated silver microparticles in which the surface of the Silver microparticles coated with gold. A method of producing a transparent conductive A layered structure according to claim 7 or 8, wherein the binder is an inorganic Binder whose main component is a silica sol. A method of producing a transparent conductive Layer structure according to claim 7 or 8, wherein the coating liquid for forming a transparent conductive layer, an inorganic binder comprises whose main component is silica sol. A coating liquid for forming a transparent coating layer used in the method of producing a transparent conductive layered structure according to claim 7, which contains as its main components a solvent, a binder and a functional group-containing compound having at least one functional group selected from mercapto groups. SH, sulfide group -S and polysulfide groups -S _x -, wherein X ≥ 2, wherein the mixing ratio of the binder and the functional group-containing compound is 0.1 to 50 parts by weight of the functional group-containing compound per 100 parts by weight of binder , The coating liquid for forming a transparent coating layer according to claim 13, wherein the binder is an inorganic binder, whose main component is silica sol. The coating liquid for forming a transparent coating layer according to claim 13 or 14, wherein the functional group-containing Compound is a compound that is hydrolyzable in its molecules Alkoxysilyl groups or produced by hydrolysis of these groups contains functional groups. A coating liquid for forming a transparent conductive layer used in the method of producing a transparent conductive layered structure according to claim 8, which comprises as its main components a solvent, gold microparticles or gold-containing noble metal microparticles containing 5% by weight or more of gold and having a functional group-containing compound having at least one functional group selected from mercapto groups -SH, sulfide group -S- and polysulfide groups -S _x -, where X≥2. The coating liquid for forming a transparent conductive A layer according to claim 16, wherein the gold content of the gold-containing Precious metal microparticles is set in a range of 50 to 95% by weight. The coating liquid for forming a transparent conductive A layer according to claim 16 or 17, wherein the gold-containing noble metal microparticles are gold-coated silver microparticles in which the surface of the Silver microparticles coated with gold. The coating liquid for forming a transparent conductive Layer according to claims 16 to 18, which contains an inorganic binder, its main component is a silica sol. The coating liquid for forming a transparent conductive Layer according to claims 16 to 19, wherein the functional group-containing compound a compound is the alkoxysilyl groups hydrolyzable in their molecules or functional groups produced by hydrolysis of this group contains. Display device comprising a device body and includes a front panel, which is arranged on the front side of the device body, wherein the transparent conductive Layer structure according to the claims 1 to 6 in the display device as a front panel with the transparent Two-layer film is installed, which is turned to the outside.